US5786400A - Process for the production of a rigid polyurethane foam and a composition for the production of a rigid polyurethane foam - Google Patents

Process for the production of a rigid polyurethane foam and a composition for the production of a rigid polyurethane foam Download PDF

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US5786400A
US5786400A US08/907,811 US90781197A US5786400A US 5786400 A US5786400 A US 5786400A US 90781197 A US90781197 A US 90781197A US 5786400 A US5786400 A US 5786400A
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polyol
rigid polyurethane
weight
polyurethane foam
parts
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Martin Brock
Mitsuaki Ikebe
Teruo Hama
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Sumika Covestro Urethane Co Ltd
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Sumitomo Bayer Urethane Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805Compounds having only one group containing active hydrogen
    • C08G18/2815Monohydroxy compounds
    • C08G18/282Alkanols, cycloalkanols or arylalkanols including terpenealcohols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805Compounds having only one group containing active hydrogen
    • C08G18/2815Monohydroxy compounds
    • C08G18/283Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4804Two or more polyethers of different physical or chemical nature
    • C08G18/482Mixtures of polyethers containing at least one polyether containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00Foam properties
    • C08G2110/0025Foam properties rigid
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes

Definitions

  • the present invention relates to a process for producing a rigid polyurethane foam, a composition for the production of a rigid polyurethane foam and the use of this rigid polyurethane foam as thermal insulation material.
  • Chlorofluorocarbons (hereinafter referred to as CFC) have hitherto been used as blowing agents for rigid polyurethane foams. Particular, trichlorofluoromethane (R11) has been used.
  • HCFC-141b (1,1-dichloro-1-fluoroethane)
  • HCFC-22 chlorodifluoromethane
  • HCFC-142b (1-chloro-1,1-difluoroethane) have been industrialized and they are already used as blowing agents for a thermal insulation.
  • the HCFC's also contain a chlorine atom in the molecule and they therefore still have the effect of depleting the ozone layer, even though the degree thereof is small.
  • the restrictions of the use of chlorine-containing compounds have been imposed and the extent of that use is being gradually reduced.
  • the use of a blowing agent having no effect on the ozone layer has recently been proposed.
  • a hydrocarbon blowing agent containing no chlorine atoms and causing no depletion of the ozone layer e.g., cyclopentane
  • Rigid polyurethane foams in which a cyclopentane has been used as the blowing agent, have good thermal insulation properties and are, therefore, widely used as thermal insulation for refrigerators, as constructional material for buildings or vehicles.
  • cyclopentane is a recommendable blowing agent since it is harmless to the global environment, its compatibility with active hydrogen compounds such as polyols is extremely poor, thus resulting in the poor long term storage stability of polyol mixtures containing cyclopentane.
  • phase stability of the polyol mixture can be improved by adding a compound such as a surface active agent as an emulsifying agent, but where conventional surface active agents such as polyoxyethylenealkylethers, polyoxyethylene phenols, alkylbenzenesulfonate salts, nonyl phenol and stearyl alcohol are used, the compatibility with the hydrocarbon blowing agent is improved but the mechanical properties of the finished polyurethane foam are impaired.
  • a compound such as a surface active agent as an emulsifying agent
  • conventional surface active agents such as polyoxyethylenealkylethers, polyoxyethylene phenols, alkylbenzenesulfonate salts, nonyl phenol and stearyl alcohol are used
  • the present invention provides a process for producing a rigid polyurethane foam comprising reacting a polyisocyanate containing a benzene ring as an organic isocyanate with a polyether polyol and/or polyester polyol in the presence of one or more catalysts, a blowing agent and optionally auxiliary substances and/or additives, characterized in that a hydrocarbon is used as the blowing agent, and a compound having a hydrophobic group and a hydroxyl group in the molecule is used as the emulsifying agent.
  • the present invention also provides a composition for the production of rigid polyurethane foams, comprising:
  • an organic isocyanate which comprises a polyisocyanate containing a benzene ring
  • an emulsifying agent which comprises a compound having a hydrophobic group and a hydroxyl group in the molecule
  • an organic polyisocyanate (2) a polyol, (3) a blowing agent, (4) an emulsifying agent and (5) a catalyst are used.
  • auxiliary substances and/or additives such as (6) water, (7) a surfactant, (8) a chain extender and/or a crosslinking agent, (9) and other additives (e.g., flame retardants and fillers) can be used.
  • organic polyisocyanate (1) a polyisocyanate such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate and polymethylenepolyphenyl polyisocyanate (polymeric MDI) and a modified polyisocyanate thereof are used alone or in the form of a mixture.
  • TDI tolylene diisocyanate
  • polymeric MDI polymethylenepolyphenyl polyisocyanate
  • a modified polyvalent isocyanate i.e., a product obtained by the partial chemical reaction of an organic di- and/or polyisocyanate can be used.
  • a di- and/or polyisocyanate containing esters, ureas, biurets, allophanates, carbodiimides, isocyanurates and/or urethane groups is used.
  • an urethane-group-containing organic, preferably, aromatic polyisocyanate having an NCO content of 33.6 to 15 wt %, preferably 31 to 21 wt % can be used, such as for example, 4,4'-diphenylmethane-diisocyanate or 2,4- or 2,6-tolylene diisocyanate, which is modified with a low-molecular-weight diol, triol, dialkylene glycol, trialkylene glycol or a polyoxyalkylene glycol having a molecular weight of not more than 1,500.
  • a di- or polyoxyalkylene glycol an individual compound or a mixture thereof can be used.
  • a diethylene-, dipropylene glycol, polyoxyethylene-, polyoxypropylene-, polyoxy-ethylene glycol or -triol can be used.
  • an NCO group-containing prepolymer having an NCO content of 25 to 9 wt %, preferably 21 to 14 wt %, based on the total weight can be used.
  • This is prepared from a mixture of the a polyester- and/or preferably polyether-polyol, with 4,4'-diphenylmethane-diisocyanate, 2,4'- and 4,4'-diphenylmethane diisocyanate, 2,4- and/or 2,6-tolylene-diisocyanate or crude MDI.
  • liquefied carbodiimide groups and/or isocyanurate group-containing polyisocyanates are preferred.
  • polyisocyanates have an NCO content of 33.6 to 15 wt %, preferably 31 to 21 wt %.
  • NCO content 33.6 to 15 wt %, preferably 31 to 21 wt %.
  • it is prepared on the basis of 4,4'-, 2,4'- and/or 2,2'-diphenylmethane-diisocyanate and/or 2,4- and/or 2,6-tolylenediisocyanate.
  • the polyol (2) is a polyether polyol or a polyester polyol.
  • the polyether polyol is prepared by adding propylene oxide (PO) and/or ethylene oxide (EO) to a starting raw material such as ethylene glycol, propylene glycol, glycerine, trimethylolpropane, pentaerythritol, triethanolamine, ethylenediamine, toluenediamine (TDA) and sugar.
  • a starting raw material such as ethylene glycol, propylene glycol, glycerine, trimethylolpropane, pentaerythritol, triethanolamine, ethylenediamine, toluenediamine (TDA) and sugar.
  • the polyether polyol can be prepared by a conventional method, for example, by adding at least one alkylene oxide containing an alkylene chain having 2 to 4 carbon atoms to a starting material containing 2 to 8, preferably 3 to 8 reactive hydrogen atoms, by anion polymerization in the presence of a catalyst, for example, an alkali hydroxide such as sodium hydroxide and potassium hydroxide or an alkaline alcoholate such as sodium methylate, sodium- or potassium ethylate or potassium isopropylate, or by cationic polymerization in the presence of a catalyst, such as for example, a Lewis acid such as pentachloroantimony and boron fluoride-etherate, or clay.
  • a catalyst for example, an alkali hydroxide such as sodium hydroxide and potassium hydroxide or an alkaline alcoholate such as sodium methylate, sodium- or potassium ethylate or potassium isopropylate, or by cationic polymerization in the presence of a catalyst, such as for example
  • alkylene oxide examples include tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, styrol oxide, and in particular, ethylene oxide, 1,2-propylene oxide, etc. These alkylene oxides can be used alone or in the term of mixtures.
  • an organic dicarboxylic acid such as succinic acid, adipic acid, phthalic acid and terephthalic acid
  • an aliphatic or aromatic substituted diamine which may be substituted with N-mono-, N,N- or N,N'-dialkyl group and has 1 to 4 carbon atoms in the alkyl chain
  • alkanolamines such as ethanolamine, diethanolamine, N-methyl- and N-ethyl-ethanolamine, N-methyl and N-ethyl-diethanolamine, triethanolamine, and ammonia.
  • a polyvalent, particularly, a trivalent and/or more valent alcohol such as ethanediol, propanediol-1,2 and propanediol-1,3, diethylene glycol, dipropylene glycol, butanediol-1,4, hexanediol-1,6, glycerine, trimethylolpropane, pentaerythritol, sorbitol and sucrose (sugar) are used.
  • the polyether polyol has functionality of preferably 3 to 8, particularly preferably 3 to 6. Its hydroxyl value is preferably from 300 to 850, particularly preferably from 350 to 800.
  • the polyester polyol, used can be produced from a polyvalent carboxylic acid and a polyvalent alcohol, such as for example, polyethylene terephthalate.
  • the preferred polyester polyol can be prepared from, for example, an organic dicarboxylic acid having 2 to 12 carbon atoms, preferably an aliphatic dicarboxylic acid having 4 to 6 carbon atoms, and a polyvalent alcohol, particularly a diol having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms.
  • dicarboxylic acid examples include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid.
  • a corresponding dicarboxylic acid derivative such as a dicarboxylic acid monoester or diester prepared by esterification with an alcohol having 1 to 4 carbon atoms or dicarboxylic anhydride can be used.
  • dihydric and polyvalent alcohol particularly the diol
  • diol examples of the dihydric and polyvalent alcohol, particularly the diol, are ethanediol, diethylene glycol, 1,2- or 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, glycerine and trimethylolpropane.
  • ethanediol diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, or a mixture prepared from at least two of the above-mentioned diols, particularly a mixture prepared from 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol are used.
  • a polyester polyol produced from a lactone such as ⁇ -caprolactone or a hydroxycarboxylic acid such as a ⁇ -hydroxycaproic acid can be used.
  • the amount of the polyol (2) used is preferably 40 to 100 parts by weight, particularly 60 to 90 parts by weight, based on 100 parts by weight of the organic isocyanate.
  • the blowing agent (3) may be a hydrocarbon having 2 to 8, particularly 4 to 6 carbon atoms (e.g., an alkane or a cycloalkane).
  • the blowing agent (3) can be selected from the group consisting of an alkane, a cycloalkane, a dialkylether, a cycloalkyleneether and a fluoroalkane (e.g., a compound having a fluorine atom and a hydrogen atom).
  • Examples of the alkane are propane, n-butane, isobutane, n-pentane, isopentane and n-hexane.
  • Examples of the cycloalkane are cyclobutane, cyclopentane, cyclohexane, cycloheptane and cyclooctane.
  • Examples of the dialkylether are dimethylether, methylethylether or diethylether.
  • An example of the cycloalkylenether is furan.
  • Examples of the fluoroalkane are trifluoromethane, difluoromethane, difluoroethane, tetrafluoroethane, heptafluoropropane, etc.
  • the blowing agent is preferably a hydrocarbon selected from a group consisting of cyclopentane, n-pentane and iso-pentane. Cyclopentane is particularly preferred.
  • the amount of blowing agent (3) used is preferably from 3 to 50 parts by weight, particularly from 5 to 40 parts by weight, based on 100 parts by weight of the organic isocyanate.
  • the compound used as the emulsifying agent (4) reacts with the isocyanate for the production of a rigid polyurethane foam. As a result, water is formed. The water formed reacts with the organic isocyanate to form carbon dioxide. The carbon dioxide gas promotes the blowing efficiency as a result of which foam density can be decreased.
  • the hydrophobic group may be a hydrocarbon group, particularly an alkyl group.
  • the number of the carbon atoms in the hydrocarbon group may be from 5 to 40, particularly from 5 to 20.
  • the hydrocarbon group is preferably branched.
  • the emulsifying agent (4) is preferably a branched hydrocarbon compound containing one hydroxyl group.
  • emulsifying agent (4) examples include n-butanol, nonyl phenol, t-butanol, lauryl alcohol and polyoxyethylenephenols. T-butanol is particularly preferred.
  • the amount of emulsifying agent used is preferably from 0.1 to 15 parts by weight, particularly from 0.2 to 5 parts by weight, based on 100 parts by weight of the organic isocyanate.
  • the catalyst (5) conventional and known amine catalysts and metallic catalysts can be used.
  • the amine catalyst are a tertiary amine such as triethylenediamine, tetramethylhexamethylenediamine, pentamethyldiethylenetriamine, dimethylcyclohexyltriamine and methyl morpholine.
  • the metallic catalyst examples include organometallic compounds such as stannous octoate, dibutyltin dilaurate and lead octylate.
  • the amount of catalyst (5) used is preferably from 0.001 to 5 parts by weight, particularly from 0.05 to 2 parts by weight, based on 100 parts by weight of the organic isocyanate.
  • the optionally used water (6) functions as a blowing agent.
  • the amount of water (6) used is preferably from 0 to 5 parts by weight, particularly from 0.5 to 3 parts by weight, based on 100 parts by weight of the organic isocyanate.
  • Organic silicone compounds can be used as the optionally used surfactant (7).
  • the amount of surfactant (7) used is preferably from 0 to 5 parts by weight, particularly from 1 to 3 parts by weight, based on 100 parts by weight of the organic isocyanate.
  • Examples of the optionally used chain extender and/or crosslinking agent (8) are an alkanolamine, and a diol and/or triol particularly having a molecular weight of not more than 400, preferably 60 to 300.
  • alkanolamine examples are ethanolamine and/or isopropanolamine.
  • dialkanolamine examples of the dialkanolamine are diethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine and diisopropanolamine.
  • trialkanolamine examples of the trialkanolamine are triethanolamine and triisopropanolamine.
  • An adduct prepared from ethylene oxide or 1,2-propylene oxide and an alkylenediamine having 2 to 6 carbon atoms in an alkylene chain such as for example, N,N'-tetra(2-hydroxyethyl)ethylene-diamine and N,N'-tetra(2-hydroxypropyl)ethylene-diamine, may be used.
  • an aliphatic, cycloaliphatic and/or aromatic diol having 2 to 14, preferably 4 to 10 carbon atoms for example, ethylene glycol, propanediol-1,3, decanediol-1,10, o-, m-, p-dihydroxycyclohexane, diethylene glycol, dipropylene glycol and preferably butanediol-1,4, hexanediol-1,6 and bis-(2-hydroxyethyl)hydroquinone, can be used.
  • 1,2,4-, 1,3,5-trihydroxycyclohexane and glycerine can, for example, be used as the tiol.
  • the amount of the chain extender and/or the crosslinking agent (8) used is preferably from 0 to 20 wt %, particularly from 2 to 5 wt % based on the polyol.
  • additives (9) are blowing stabilizers, foam controlling agents, fillers, dyes, pigments, flame retardants, hydrolysis inhibitors, mildewproofing agents, bactericides and the like.
  • the amount of additive (9) used is preferably from 1 to 40 parts by weight, particularly from 5 to 20 parts by weight, based on 100 parts by weight of the organic polyisocyanate.
  • Examples of the filler are carbon black and calcium carbonate.
  • Suitable flame retardant are tricresyl phosphate, tris-(2-chloroethyl)phosphate, tris-(2-chloropropyl)phosphate, tris-(1,3-dichloropropyl)phosphate, tris-(2,3-dibromopropyl) phosphate, tetrakis-(2-chloroethyl)-ethylenediphosphate etc.
  • an inorganic flame retardant such as red phosphorus, aluminum oxide hydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate
  • a cyanuric acid derivative such as melamine or a mixture of at least two kinds of flame retardants, such as for example, an ammonium polyphosphate and melamine.
  • the equivalent ratio of the isocyanate group in the polyisocyanate to the reactive hydrogen atom of the polyol, the emulsifying agent and the chain extender and/or the crosslinking agent is 0.85 to 1.25:1, preferably 0.95 to 1.15:1, particularly favorably 1.0 to 1.10:1.
  • the rigid polyurethane foam can be prepared by a non-continuous process or continuous process, by a prepolymer process, or a one shot foaming process using known mixing equipment.
  • component (A) is composed of the organic polyisocyanate and component (B) is composed of the remaining constituents other than the organic polyisocyanate (1).
  • the starting raw material components are mixed at 15° to 90° C., preferably 20° to 35° C., and introduced into an open molding machine in which the temperature can be controlled.
  • the reaction mixture was blown without pressure in order to avoid peripheral compression.
  • a foamable reaction mixture is suitably injected or sprayed on the back of the surface layer and blown to from a cured rigid polyurethane foam.
  • the rigid polyurethane foam preferably has a density of 20 to 100 kg/m 3 and a thermal conductivity of 0.0140 to 0.0230 kcal/mh°C.
  • the rigid polyurethane foams produced according to the invention can be used as thermal insulation material, e.g. as an intermediate layer in a thermally insulating laminated composite material, an injectable foam for filling the hollow space inside a cooling-and-freezing device, in particular, a refrigerator or a freezer, a thermal insulation jacket for containers for the storage of hot water or the thermal insulation of articles to be heated.
  • a cooling-and-freezing device in particular, a refrigerator or a freezer
  • a thermal insulation jacket for containers for the storage of hot water or the thermal insulation of articles to be heated.
  • a mixed polyol liquid was prepared by mixing an amine catalyst (N,N-dimethylcyclohexylamine) (the amount required for adjusting the reactive gel time to approximately 50 seconds), 2 parts by weight of a surfactant (L-5421, manufactured by Nippon Unicar Co., Ltd.) and 0.5 parts by weight of water with 50 parts by weight of polyol A, 30 parts by weight of polyol B and 20 parts by weight of polyol C.
  • the mixed polyol liquid t-Butanol or polyoxyethylene nonyl phenol w as added as emulsifying agent and cyclopentane as the blowing agent in order to prepare a polyol mixture.
  • Polyol A A polyol having a hydroxyl value of 450 mg KOH/g and obtained by the addition of propylene oxide (PO) using sugar as a starting raw material.
  • PO propylene oxide
  • Polyol B A polyol having a hydroxyl value of 400 mg KOH/g and obtained by the addition of PO using toluenediamine (TDA) as a starting raw material.
  • Polyol C A polyol having a hydroxyl value of 380 mg KOH/g and obtained by the addition of PO using ethylenediamine as a starting raw material.
  • the above-mentioned polyol mixture (comprising the mixed polyol liquid, cyclopentane, t-butanol or polyoxyethylene nonyl phenol) and polymeric MDI were mixed by a mixer.
  • the temperature of the urethane raw material was adjusted to 20° C.
  • a rigid polyurethane foam obtained by stirring and mixing the urethane mixture liquid was introduced into a mold made of aluminum and having a size of 600 mm ⁇ 400 mm ⁇ 50 mm. Seven minutes later, the molded article was removed from the mold.
  • the foam properties of the demolded article are shown in Table 2.
  • Foam density was measured when carrying out free foaming in a box made of veneered material, of which the internal dimension is 150 mm ⁇ 300 mm ⁇ 150 mm.
  • a 50 mm cubic sample cut from the core portion of a foam was compressed toward a direction vertical to a stream.
  • a stress (10 mm/min. head speed) was measured when its displacement reached 10%.
  • the rate of dimensional deformation was measured when a 50 mm cubic sample cut from the core portion of a foam was retained at -30° C. for 48 hours.
  • the solubility of a blowing agent such as cyclopentane is improved. Accordingly, the long term storage stability of a polyol mixture containing a blowing agent is improved. Also, it is possible to maintain good thermal conductivity and high mechanical strength of a thermal insulation material.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
US08/907,811 1996-08-13 1997-08-08 Process for the production of a rigid polyurethane foam and a composition for the production of a rigid polyurethane foam Expired - Lifetime US5786400A (en)

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JP08213512A JP3105793B2 (ja) 1996-08-13 1996-08-13 硬質ポリウレタンフォームの製造方法および硬質ポリウレタンフォーム用組成物
JP8-213512 1996-08-13

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US (1) US5786400A (ko)
EP (1) EP0824123A1 (ko)
JP (1) JP3105793B2 (ko)
KR (1) KR19980018592A (ko)
CN (1) CN1176968A (ko)
BR (1) BR9704347A (ko)
CA (1) CA2212914A1 (ko)
CZ (1) CZ253097A3 (ko)
HU (1) HUP9701385A3 (ko)
PL (1) PL321563A1 (ko)
SK (1) SK107297A3 (ko)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6420443B1 (en) 1999-09-09 2002-07-16 Crompton Corporation Additives for enhanced hydrocarbon compatibility in rigid polyurethane foam systems
WO2003099893A1 (en) * 2002-05-23 2003-12-04 Bayer Materialscience Llc Rigid polyurethane foams for insulation and process for producing same
US20050070618A1 (en) * 2003-09-26 2005-03-31 Miller John William Blowing agent enhancers for polyurethane foam production
US20050159498A1 (en) * 2003-08-29 2005-07-21 Bradford Larry L. Flame retardant composition and polyurethane foam containing same
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US20070155845A1 (en) * 2003-08-29 2007-07-05 Emmanuel Pinzoni Non-halogenated flame retardent composition and polyurethane foam containing same
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RU2621188C2 (ru) * 2011-08-23 2017-06-01 Басф Се Микроэмульсии
CN109153762A (zh) * 2016-05-17 2019-01-04 东曹株式会社 用于制造卤代烯烃发泡聚氨酯的胺催化剂组合物

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US20070155845A1 (en) * 2003-08-29 2007-07-05 Emmanuel Pinzoni Non-halogenated flame retardent composition and polyurethane foam containing same
US20050159498A1 (en) * 2003-08-29 2005-07-21 Bradford Larry L. Flame retardant composition and polyurethane foam containing same
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US9321892B2 (en) 2003-09-26 2016-04-26 Air Products And Chemicals, Inc. Blowing agent enhancers for polyurethane foam production
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US20050070619A1 (en) * 2003-09-26 2005-03-31 Miller John William Blowing agent enhancers for polyurethane foam production
US20090312447A1 (en) * 2006-02-15 2009-12-17 Stepan Company Compatibilizing surfactants for polyurethane polyols and resins
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US20130217797A1 (en) * 2011-08-23 2013-08-22 Basf Se Microemulsions
RU2621188C2 (ru) * 2011-08-23 2017-06-01 Басф Се Микроэмульсии
US20150183949A1 (en) * 2012-06-15 2015-07-02 Bayer Materialscience Ag Microcellular polyurethane composition, method of preparation and uses thereof
CN109153762A (zh) * 2016-05-17 2019-01-04 东曹株式会社 用于制造卤代烯烃发泡聚氨酯的胺催化剂组合物
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CN109153762B (zh) * 2016-05-17 2021-04-02 东曹株式会社 用于制造卤代烯烃发泡聚氨酯的胺催化剂组合物

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EP0824123A1 (en) 1998-02-18
CN1176968A (zh) 1998-03-25
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JP3105793B2 (ja) 2000-11-06
SK107297A3 (en) 1999-03-12
MX9706139A (es) 1998-08-30
CA2212914A1 (en) 1998-02-13
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HU9701385D0 (en) 1997-10-28
HUP9701385A2 (hu) 1998-04-28

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